US2664428A - delta-17 alpha-hydroxy-3,20-diketo-pregnen-21-als - Google Patents
delta-17 alpha-hydroxy-3,20-diketo-pregnen-21-als Download PDFInfo
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- US2664428A US2664428A US243914A US24391451A US2664428A US 2664428 A US2664428 A US 2664428A US 243914 A US243914 A US 243914A US 24391451 A US24391451 A US 24391451A US 2664428 A US2664428 A US 2664428A
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- diketo
- parts
- pregnen
- hydroxy
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 2
- 150000002832 nitroso derivatives Chemical class 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 1
- BCMVQWBCTDGFQA-PAPGYHMHSA-N 2-[(8R,9S,10S,13S,14S)-10,13-dimethyl-3-oxo-1,2,4,5,6,7,8,9,11,12,14,15-dodecahydrocyclopenta[a]phenanthren-17-yl]-2-oxoacetaldehyde Chemical compound O=C1CC2CC[C@H]3[C@@H]4CC=C(C(C=O)=O)[C@]4(CC[C@@H]3[C@]2(CC1)C)C BCMVQWBCTDGFQA-PAPGYHMHSA-N 0.000 description 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000006286 aqueous extract Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AOJDZKCUAATBGE-UHFFFAOYSA-N bromomethane Chemical compound Br[CH2] AOJDZKCUAATBGE-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- UJYKADYTQMVUAG-UHFFFAOYSA-N n-[[4-(dimethylamino)phenyl]methylidene]hydroxylamine Chemical compound CN(C)C1=CC=C(C=NO)C=C1 UJYKADYTQMVUAG-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- -1 p-dimethylamino-phenyl Chemical group 0.000 description 1
- 150000003129 pregnenals Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J43/00—Normal steroids having a nitrogen-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J5/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
Definitions
- a -17/3-hydrox-y-3,20 diketoepregnenemrals. are. already known. In these known aldehydes, the.
- the A -17a-hydroxy-3,20 diketo.- pregnen-Zlals of the present invention are obtained by reacting anorganic nitroso compound with a quaternary A' -l7a-hydroxy-3,2Q-diketo pregnen-2lyl-ammonium compound, and then liberating the desired aldehyde from the nitrone thus obtained.
- nitrones such as IliUT benzene and dialk ylam no -nitrosoebenzenes, for example p-dimethylamino-nitroso-benzene.
- the production of the nitrones takes place in the presence. of an alkaline agent. burprisingly, the condensation may, becarried out in excellent yield even in the presence of a bicarbonate of an alkali metal, as for example potassium bicarbonate.
- the aldehyde may be liberated by treatment with an acid agent.
- an acid agent such as pyroracemic acid.
- Example 1 oil with suction, washed with Example 1 4.90 parts by weight of A -17ahydroxy-3,20.- diketo-pregnen-Zl-yl-pyridinium bromide:
- a -l7a-hydroxy-3,20 diketo pregnen-Zlyl-pyridinium bromide used as starting material in this example, is prepared for instance as follows:
- CH2Br are mixed with 7.5 parts by volume of dry pyridine and maintained for 2a hours at room temperature with occasional stirring.
- the excess of pyridine is then distilled oi as completely as possible under reduced pressure, the formed crystallizate stirred with a parts by volume of methanol and, after 2 hours, the mother liquor filtered with suction followed by washing of the collected crystals with a little ice cold methanol.
- the pure pyridinium salt is obtained as colorless flat prisms which melt at 285-287 C. (with decomposition and brown diszoloration above 178 C.).
- the aforementioned Zl-bromo-pregnene itself can be obtained for example by treatment of A B-keto-Zl-bromo pregnadiene with hydrogen peroxide in the presence or" osmium tetroxide.
- Example 2 21.9 parts by weight of A -1'7a-hydroxy-3,20- diketo-pregnen-2l yl-pyridinium chloride:
- Example 1 The further working up follows as described in Example 1.
- the (A -l7a-hydroxy-3-keto-aetiocholenoyl) N (p-dimethylamino phenyl) -nitrone oota.ned is identical with that described in Example 1.
- a -17a-hydroxy-3,ZO-diketo pregnen-Zlyl-pyridinium chloride used as starting material in this example is prepared, for instance, as follows:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Description
Patented Dec. 29, 1953 AMu-HYDRQXY-se O-DSIKETO-PREGNEN- 7 Karl Miesclien fihine, and Julius Schmidlin,
. B s witz erlan'd, assignors to Ciba Pharmaceutical ifrod ict s', Ina, Summit, N. J.
- NoDrawing..,Application August 27, 1951,
1' seal-N 243,914 f Claims priority,-application Switzerland September 12.1951) l he present inventionrelatesto A al'laehye droxy-3,-20-diketo-pregnen21-als. and to the preparation thereof. These n elhrhydroxya 3,20-dilreto-pregnen-2l-als may contain addie ticnal free or functionally comerted. hydroxyer keto groups, particularly in the ll-position, orv
may also contain additional doublebonds, asfor example in the 9,11- or 11-,l2-position.
A -17/3-hydrox-y-3,20 diketoepregnenemrals. are. already known. In these known aldehydes, the.
side chain possesses the configuration which results from the reaction of a 1-7-ketonenwith, for example, an organometallic' compound. Compared with these known substances, the pregnenals of the present invention-and especially A l'la-hydroxy 3,20 diketo-pregnen-Zl-al itselfpossess very valuable suprarenal cortex hormone activities. For medical use the new compounds are transformed into tablets or injectable solutions. 1
The A -17a-hydroxy-3,20 diketo.- pregnen-Zlals of the present invention are obtained by reacting anorganic nitroso compound with a quaternary A' -l7a-hydroxy-3,2Q-diketo pregnen-2lyl-ammonium compound, and then liberating the desired aldehyde from the nitrone thus obtained.
As starting materials there are employed espe-. cially quaternary ammonium salts which are derived from heterocyclic basesof aromatic character, such as pyridine, quinoline and isoquinoe line. These startingmaterials are obtained by reaction of the appropriate tertiary amine 'with an ester of the corresponding 2l-hy droxyepregenl a p-Q ad d as e qr a fii d s as a hydrohalio acid or an organic sul fohic acid. Forthe interaction with the quaternary ammonium salt, use is preferably made of a nitroso compound of the aromatic series. suchas IliUT benzene and dialk ylam no -nitrosoebenzenes, for example p-dimethylamino-nitroso-benzene. The production of the nitrones takes place in the presence. of an alkaline agent. burprisingly, the condensation may, becarried out in excellent yield even in the presence of a bicarbonate of an alkali metal, as for example potassium bicarbonate. From the nitrone obtained according to this process, the aldehyde may be liberated by treatment with an acid agent. The same, result is achieved however also by reaction with a carbonyl compound, such as pyroracemic acid.
The following examples illustrate the invention, the relation between parts by Weight and parts by volume being the same as that between the gram and milliliter.
, oil with suction, washed with Example 1 4.90 parts by weight of A -17ahydroxy-3,20.- diketo-pregnen-Zl-yl-pyridinium bromide:
' OH i )3" p6 and 1.55 parts by weight of pnitroso-dimethylaniline are dissolved in parts by volume of methanol with addition oflOO parts by volume of water and mixed with a solution of 1.02 parts by weight of potassium bicarbonate in 50 parts by volume of water. After being kept for 6 days at room temperature'with occasional agitation, the small red plates which have separated are filtered 50 per cent, methanol and then dried. By recrystallization from methylene chloride-methanol, there is obtained the pure (A -l'la-hydroxy-t-keto-aetiocholenoyl)-N(p-dimethylamino-phenyl)-nitrone of the formula:
CH3 CO which melts at 182 C. (with decomposition).
4.80 parts by weight of the thus-obtained (A l'la-hydroxy 3 ketc aetiocholenoyl) -N-(p-dimethylamino-phenyl)-nitrone are covered with 2500 parts by volume of ether and the suspension shaken for 2 hours with 500 parts by volumeof l-normal hydrochloric acid. The aqueous phase is then separated off and the ether solution washed consecutively with l-normal hydrochloric acid, water, 2 percent. sodium bicarbonate solution and water. The aqueous extracts, before being discarded, are extracted several times with ether. The dried ethereal solution is gradually evaporated to about 20 parts by volume whereby in most cases crystallization begins without seeding. The practically colorless substance thus obtained is easily isolated by suction filtration, and is then washed with ether. In this way, there obtained A -l7whydroxy 3,20 diketo-pregnen- 21-al:
CHO
as a hydrate which melts at lO-l08 C. (with decomposition) and which has the rotation [a] =+1l1i2 (C=l.036 in dioxane).
In analogous manner A and A -17ahydroxy-3,20-diketo-pregnadiene-2l-al are prepared.
The A -l7a-hydroxy-3,20 diketo pregnen-Zlyl-pyridinium bromide, used as starting material in this example, is prepared for instance as follows:
1.85 parts by weight of finely powdered A -17ahydroxy-3,20-diketo-2l-bromopregnene:
CH2Br are mixed with 7.5 parts by volume of dry pyridine and maintained for 2a hours at room temperature with occasional stirring. The excess of pyridine is then distilled oi as completely as possible under reduced pressure, the formed crystallizate stirred with a parts by volume of methanol and, after 2 hours, the mother liquor filtered with suction followed by washing of the collected crystals with a little ice cold methanol. By recrystallization from boiling methanol, the pure pyridinium salt is obtained as colorless flat prisms which melt at 285-287 C. (with decomposition and brown diszoloration above 178 C.). The aforementioned Zl-bromo-pregnene itself can be obtained for example by treatment of A B-keto-Zl-bromo pregnadiene with hydrogen peroxide in the presence or" osmium tetroxide.
Example 2 21.9 parts by weight of A -1'7a-hydroxy-3,20- diketo-pregnen-2l yl-pyridinium chloride:
co 1 on water, and the resultant solution admixed with a solution of 4.08 parts by weight of potassium bicarbonate in 200 parts by volume of water. The further working up follows as described in Example 1. The (A -l7a-hydroxy-3-keto-aetiocholenoyl) N (p-dimethylamino phenyl) -nitrone oota.ned is identical with that described in Example 1.
2.40 parts by weight of finely powdered pure (A -l'la-hydroxy 3 -.keto-aetiocholenoyl) -N-(pdimethylamino-phenyl)-nitrone are suspended in 500 parts by volume of ether and shaken with a solution of 8.80 parts by weight of pyroracemic acid in 250 parts by volume of water for 10 days in a nitrogen atmosphere. The ether solution is then separated from the dark red aqueous layer, the latter being further twice extracted with fresh ether before being discarded. The ether solutions are then washed consecutively with water, 2 per cent. sodium carbonate solution and water, then combined and dried with sodium sulfate. By carefully distilling off the ether, there is obtained the A -l7a-hydroxy-3,20-diketo-pregnen-2l-al as the hydrate which melts at 108 C. (with decomposition) as described in Example 1. l
The A -17a-hydroxy-3,ZO-diketo pregnen-Zlyl-pyridinium chloride used as starting material in this example is prepared, for instance, as follows:
6.93 parts by weight of M-l'lazl-dihydroxy- 3,20-diketo-pregnene-(R-eichsteins Substance S) "onion .CHs.. .IQO V I [OH i D are dissolved, with exclusion of moisture, in 50 parts by volume of dry pyridine, 4.80 parts by weight of pure p-tosyl chloride added and, after agitation for a short time, the reaction mixture kept for 12 days in the dark. Then excess pyridine is removed under reduced pressure at room temperature, the formed crystals stirred with 43 parts by volume of acetone and, after several hours standing, the crystals isolated by suction filtration. By recrystallization from methanol, while decolorizing with activated carbon, and by displacing the methanol by means of 96 per cent. ethanol, the pure pyridinium is obtained from the crude salt mixture as colorless platelets which melt at 304-30? C. (with decomposition).
What is claimed is:
l. A A -17a-hydroxy-3,ZO-diketo-pregnen- 21- a1.
2. A -l'la-hydroxy-3,20-diketo-pregnen-2l-al.
KARL MIESCHER. A .aJULIUS SCHMIDLIN.
Name Date Miescher Mar. 10, 1942 Number
Claims (1)
1. A $1-17A-HYDROXY-3,20-DIKETO-PREGNEN-21AL.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2664428X | 1950-09-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2664428A true US2664428A (en) | 1953-12-29 |
Family
ID=4570920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US243914A Expired - Lifetime US2664428A (en) | 1950-09-12 | 1951-08-27 | delta-17 alpha-hydroxy-3,20-diketo-pregnen-21-als |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2664428A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2920084A (en) * | 1956-04-02 | 1960-01-05 | Olin Mathieson | 21-nitrones of 9-halo-pregnenes |
| US2920999A (en) * | 1957-06-07 | 1960-01-12 | Pfizer & Co C | 21-nitrogen derivatives of corticosteroids |
| US2951856A (en) * | 1954-07-29 | 1960-09-06 | Lab Francais Chimiotherapie | Process of dehydrobrominating keto steroids and products obtained thereby |
| US3022296A (en) * | 1956-04-02 | 1962-02-20 | Olin Mathieson | Synthesis of steroids |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2275790A (en) * | 1938-07-01 | 1942-03-10 | Ciba Pharm Prod Inc | Aldehydes of the saturated and unsaturated pregnane-series and process of making same |
-
1951
- 1951-08-27 US US243914A patent/US2664428A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2275790A (en) * | 1938-07-01 | 1942-03-10 | Ciba Pharm Prod Inc | Aldehydes of the saturated and unsaturated pregnane-series and process of making same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2951856A (en) * | 1954-07-29 | 1960-09-06 | Lab Francais Chimiotherapie | Process of dehydrobrominating keto steroids and products obtained thereby |
| US2920084A (en) * | 1956-04-02 | 1960-01-05 | Olin Mathieson | 21-nitrones of 9-halo-pregnenes |
| US3022296A (en) * | 1956-04-02 | 1962-02-20 | Olin Mathieson | Synthesis of steroids |
| US2920999A (en) * | 1957-06-07 | 1960-01-12 | Pfizer & Co C | 21-nitrogen derivatives of corticosteroids |
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